US2561483A - Method for preparing isoprene by dehydration of 1-methoxy, 3-methyl, butene-3 - Google Patents
Method for preparing isoprene by dehydration of 1-methoxy, 3-methyl, butene-3 Download PDFInfo
- Publication number
- US2561483A US2561483A US96625A US9662549A US2561483A US 2561483 A US2561483 A US 2561483A US 96625 A US96625 A US 96625A US 9662549 A US9662549 A US 9662549A US 2561483 A US2561483 A US 2561483A
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- Prior art keywords
- methyl
- isoprene
- butene
- methoxy
- dehydration
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
- C07C2521/04—Alumina
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/12—Silica and alumina
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/02—Sulfur, selenium or tellurium; Compounds thereof
- C07C2527/053—Sulfates or other compounds comprising the anion (SnO3n+1)2-
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/14—Phosphorus; Compounds thereof
- C07C2527/16—Phosphorus; Compounds thereof containing oxygen
- C07C2527/167—Phosphates or other compounds comprising the anion (PnO3n+1)(n+2)-
Definitions
- hydrochloric acid and methyl alcohol recombine to a large extent to form unusable methyl chloride and water.
- the hydrochloric acid causes corrosion, and this poses complicated equipment problems.
- This reaction is carried out in the vapor phase at atmospheric or reduced pressure. In a preferred embodiment of the invention, the reaction is conducted under a vacuum of about to 100 mm. Hg.
- the various known dehydration catalysts may be used in connection with the above reaction.
- Such catalysts may include metal oxides such as alumina, silicates such as aluminum silicate, or mixtures thereof alone or further in admixture with phosphates such as copper phosphate, or sulphates such as magnesium, lead and barium sulphates.
- metal oxides such as alumina, silicates such as aluminum silicate, or mixtures thereof alone or further in admixture with phosphates such as copper phosphate, or sulphates such as magnesium, lead and barium sulphates.
- aluminum phosphate may be used as a catalyst alone.
- the method described provides a yield in isoprene closely approaching on the theoretical yield, reaching a value as high as to 98%.
- the hydrochloric acid formed in the de-hydrochlorination of the chloro-iso-amyl-methyl ether is separated and collected separately, so that due to its absence from the reaction medium corrosion is eliminated.
- the resulting isoprene is pure and readily polymerizable, the catalyst does not become obstructed and its useful life is considerably lengthened.
- Example ,7 Iso amylene methyl ether (prepared as afore-described) is delivered through a capillary tube at a rate of 500 grams per hour into, a furnace heated at 310 0., and containing 1 liter of a catalyst comprising kaolin with 5% by weight of copper phosphate and maintained under a vacuum of about 60 mm. Hg.
- the catalyst is employed in the form of small cylinders or rodlike pellets (about 3 mm. in diameter and to mm. long). To obtain the catalyst in this form,
- the finely pulverised kaolin is diluted in water together with ground copper phosphate; the resulting paste is then extruded through a calibrated tube and is dried in the presence of air at a temperature of 20 C. until it has set.
- the electrically heated furnace is slightly inclined with respect to a horizontal plane and the 7-150- amylene-methyl ether is delivered into the top thereof.
- the gases discharged from the furnace are dried in a drying column provided with an anhydrous calcium chloride filling and are then condensed in a container cooled with liquid air and are subjected to fractional distillation.
- Method of preparing isoprene which comprises passing 1-methoxy', B-methyl, butene-3 in the vapor phase, over a dehydration catalyst comprising kaolin containing 5% by weight of copper phosphate therein, at a temperature of about 310 C. and at a reduced pressure of about 60 mm. Hg., condensing the reaction products and subjecting the condensate to fractional distillation.
Description
Patented July 24, 1951 N bFF C METHOD FOR PREPARING ISOPRENE BY D E- HYDRATION or l-METHOXY, Y3-METHYL,
BUTENE-3 Marius Sean, Montreuil-sou s-Bois, and- Isidor v Raitzyn, Belloy, France; assignors to Com pagnie dc Produits Chimiques et Elc'ctrometallurgiques Alais Froges, France, a French society a ct Camargue, .Paris',
No Drawing. Application June 1, 1949,Serial1No'. 96,625. In France July 27, 1948 This invention relates to the preparation of isoprene. v The provision of a method of preparing 'isoprene by means of a simple reaction with high yields is highly desirable from a commercial standpoint. A method of preparing isoprene has already been proposed which is based on a thermal decomposition reaction of chloroi'so'amylmethyl-ether, which comprises causing the vapors of said ether to pass over a catalyst comprising barium chloride deposited on asuitable support such as silica, heated at about 310 C. The resulting decomposition reaction leads to the simultaneous formation of hydrochloric acid, methyl alcohol and isoprene according to the equation:
CH CH3 C GLOBE-(EH20 CH5 H (DH-CH3 OH+ CH2: l-CH-CH: C s
This procedure however has a number of shortcomings. In the first place, the yield in isoprene is not above 70% of the quantitative yield as calculated from the above formula. Then, the catalyst becomes clogged up or obstructed at the end of a short time, and it cannot be subjected to a regeneration treatment by steam and a stream of air more than a given number of times. The resins and other carbonaceous deposits which impregnate the catalyst cause its efiiciency to drop off sharply.
The hydrochloric acid and methyl alcohol recombine to a large extent to form unusable methyl chloride and water. In the presence of the water thus formed, the hydrochloric acid causes corrosion, and this poses complicated equipment problems.
Secondary reactions, especially the formation of chlorinated compounds such as 2-chloro-2- methyl-butene-3 cause a reduction in yield and make it difiicult to purify the resulting isoprene product.
It is a general object of the invention to eliminate the above shortcomings of prior isoprene production methods of the type described.
It has been stated by applicants in their copending U. S. patent application Ser. No. 96,623, filed June 9, 1949, that the reaction occurring when chloro-iso-amyl-methyl ether vapors are passed over bariumsulphate as catalyst results in the production'of. h-ydrochloricacid and a new product, l-methoxy, 3-methyl, butene-3, according to the reaction:
This reaction is carried out in the vapor phase at atmospheric or reduced pressure. In a preferred embodiment of the invention, the reaction is conducted under a vacuum of about to 100 mm. Hg.
The various known dehydration catalysts may be used in connection with the above reaction. Such catalysts may include metal oxides such as alumina, silicates such as aluminum silicate, or mixtures thereof alone or further in admixture with phosphates such as copper phosphate, or sulphates such as magnesium, lead and barium sulphates. Also aluminum phosphate may be used as a catalyst alone.
The method described provides a yield in isoprene closely approaching on the theoretical yield, reaching a value as high as to 98%. The hydrochloric acid formed in the de-hydrochlorination of the chloro-iso-amyl-methyl ether is separated and collected separately, so that due to its absence from the reaction medium corrosion is eliminated. The resulting isoprene is pure and readily polymerizable, the catalyst does not become obstructed and its useful life is considerably lengthened.
Example ,7 Iso amylene methyl ether (prepared as afore-described) is delivered through a capillary tube at a rate of 500 grams per hour into, a furnace heated at 310 0., and containing 1 liter of a catalyst comprising kaolin with 5% by weight of copper phosphate and maintained under a vacuum of about 60 mm. Hg. The catalyst is employed in the form of small cylinders or rodlike pellets (about 3 mm. in diameter and to mm. long). To obtain the catalyst in this form,
the finely pulverised kaolin is diluted in water together with ground copper phosphate; the resulting paste is then extruded through a calibrated tube and is dried in the presence of air at a temperature of 20 C. until it has set. The electrically heated furnace is slightly inclined with respect to a horizontal plane and the 7-150- amylene-methyl ether is delivered into the top thereof. The gases discharged from the furnace are dried in a drying column provided with an anhydrous calcium chloride filling and are then condensed in a container cooled with liquid air and are subjected to fractional distillation.
A theoretical yield is thus collected of isoprene and methyl oxide, which last-named compound results from the secondary reaction .mixtures of aluminum silicates with metal phos- I 4 phates and metal sulphates, at a temperature within the range of from about 220 C. to about 430 C., condensing the reaction product and subjecting the condensate to fractional distillation. 2. Method of preparing isoprene as in claim 1,
wherein said reaction is operated in vacuo at a.
pressure within the range of about to mm. Hg. 7 3. Method of preparing isoprene which comprises passing 1-methoxy', B-methyl, butene-3 in the vapor phase, over a dehydration catalyst comprising kaolin containing 5% by weight of copper phosphate therein, at a temperature of about 310 C. and at a reduced pressure of about 60 mm. Hg., condensing the reaction products and subjecting the condensate to fractional distillation.
4. Method as in claim 3 wherein said catalyst is in the form of rodlike pellets.
MARIUS sEoN. ISIDOR RAITZYN.
REFERENCES CITED The following references are of record in the file of this patent:
UNITED STATES PATENTS (Addition to 13,327/ 13) OTHER REFERENCES Egloff et al.: Methods of Preparing Butadiene,
- Oil and Gas Journal, December 17, 1942, pages
Claims (1)
1. METHOD OF PREPARING ISOPRENE WHICH COMPRISES PASSING 1-METHOXY, 3-METHYL, BUTENE-3 IN THE VAPOR PHASE OVER A DEHYDRATION CATALYST SELECTED FROM THE GROUP CONSISTING OF ALUMINA, ALUMINUM PHOSPHATE, ALUMINUM SILCATES, AND MIXTURES OF ALUMINUM SILICATES WITH METAL PHOSPHATES AND METAL SULPHATES, AT A TEMPERATURE WITHIN THE RANGE OF FROM ABOUT 220* C. TO ABOUT 430* C., CONDENSING THE REACTION PRODUCT AND SUBJECTING THE CONDENSATE TO FRACTIONAL DISTILLATION.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR2561483X | 1948-07-27 |
Publications (1)
Publication Number | Publication Date |
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US2561483A true US2561483A (en) | 1951-07-24 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US96625A Expired - Lifetime US2561483A (en) | 1948-07-27 | 1949-06-01 | Method for preparing isoprene by dehydration of 1-methoxy, 3-methyl, butene-3 |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2739995A (en) * | 1951-06-29 | 1956-03-27 | Gen Aniline & Film Corp | Preparation of conjugated dienes |
US3082272A (en) * | 1958-10-10 | 1963-03-19 | Exxon Research Engineering Co | Process for methylating olefins |
US3674889A (en) * | 1970-06-23 | 1972-07-04 | Ethyl Corp | Preparation of olefins via pt-sn catalyst |
EP0030109A1 (en) * | 1979-12-04 | 1981-06-10 | Kuraray Co., Ltd. | Process for producing isoprene |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB191313327A (en) * | 1912-09-23 | 1913-08-21 | James Yate Johnson | Improvements in the Manufacture and Production of Isoprene. |
GB191408782A (en) * | 1914-04-07 | 1915-02-18 | John Henry George Hayman | Improvements in and relating to Road Wheels for Motor and like Vehicles. |
US2427704A (en) * | 1945-03-20 | 1947-09-23 | Celanese Corp | Process for the production of butadiene |
-
1949
- 1949-06-01 US US96625A patent/US2561483A/en not_active Expired - Lifetime
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB191313327A (en) * | 1912-09-23 | 1913-08-21 | James Yate Johnson | Improvements in the Manufacture and Production of Isoprene. |
GB191408782A (en) * | 1914-04-07 | 1915-02-18 | John Henry George Hayman | Improvements in and relating to Road Wheels for Motor and like Vehicles. |
US2427704A (en) * | 1945-03-20 | 1947-09-23 | Celanese Corp | Process for the production of butadiene |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2739995A (en) * | 1951-06-29 | 1956-03-27 | Gen Aniline & Film Corp | Preparation of conjugated dienes |
US3082272A (en) * | 1958-10-10 | 1963-03-19 | Exxon Research Engineering Co | Process for methylating olefins |
US3674889A (en) * | 1970-06-23 | 1972-07-04 | Ethyl Corp | Preparation of olefins via pt-sn catalyst |
EP0030109A1 (en) * | 1979-12-04 | 1981-06-10 | Kuraray Co., Ltd. | Process for producing isoprene |
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